Treatment of the Schiff base ligands a-f with Li2[PdCl4]/NaAcO in methanol under reflux gave the single nuclear palladacycles 1a-1f, with the metal atom bonded to a terdentate monoanionic [C,N,S] iminic ligand and to a chloride ligand that completes the palladium coordination sphere. Reaction of 1a-1c with silver perchlorate/triphenylphosphine in acetone at room temperature yielded the single nuclear complexes 2a-2c as the perchlorate salts, after substitution of the chloride ligand by a triphenylphosphine. However, reaction of a-c with Na2[PdCl4]/NaAcO in methanol at room temperature also gave compounds 1a-1c albeit contaminated with small amounts of the corresponding free aldehyde (mixture A). Reaction of mixture A with silver perchlorate/triphenylphosphine in acetone at room temperature gave analogously 2a-2c with some of the corresponding free aldehyde (mixture B). Attempts to purify mixtures A and B via recrystallization produced single crystals of 5 and 6 respectively: two serendipitously formed complexes, bearing thiomethyl aniline and/or acetate ligands, and void of aldehyde or iminic residue; the structures contain eight- and six-membered rings of alternating palladium and nitrogen atoms, respectively. To clarify this situation the aniline itself was reacted with palladium(II) acetate or with Na2[PdCl4]; in the latter case after recrystallization a unique behavior is revealed, giving rise to a tetranuclear complex containing a Pd4N4 ring with three differing coordination environments on the palladium atoms. Treatment of 1d with Ph2PCH2PPh2 (dppm)/AgClO4 or with Ph2PCH2(PPh2)W(CO)5/AgClO4 gave 3d, with a mono-coordinated dppm ligand, and 4d, respectively; complex 3d could not be converted into 4d by reaction with W(CO)5(THF). Recrystallization of 4d gave a still further noticeable species, complex 8: a pentanuclear trans-configured heterometallic mixed valent Pd(II)/W(0) linear complex with the palladium atoms supported by two acetate and two thiomethyl aniline bridging ligands. The complexes were fully characterized by microanalysis, IR, 1H, and 31P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 1b, 5, 6, 7 and 8 are described.